Process for the preparation of (co)polymers of conjugated dienes in the presence of a catalytic system comprising an oxo-nitrogenated complex of cobalt

Patent metadata

Field	Value
Publication number	US-9562120-B2
Application number	US-201314442598-A
Country	US
Kind code	B2
Filing date	Dec 13, 2013
Priority date	Dec 20, 2012
Publication date	Feb 7, 2017
Grant date	Feb 7, 2017

Abstract

Process for the preparation of (co) polymers of conjugated dienes which comprises polymerizing at least one conjugated diene in the presence of a catalytic system comprising at least one oxo-nitrogenated complex of cobalt having general formula (I), wherein: —R 1 and R 2 , equal to or different from each other, represent a hydrogen atom; or they are selected from linear or branched C 1 -C 20 , preferably C 1 -C 15 , alkyl groups, optionally halogenated; cycloalkyl groups optionally substituted; aryl groups optionally substituted; —Y represents an oxygen atom; or a group —N—R 3 wherein R 3 represents a hydrogen atom, or it is selected from linear or branched C 1 -C 20 preferably C 1 -C 15 , alkyl groups, optionally halogenated, cycloalkyl groups optionally substituted-; aryl groups optionally substituted; or, when Y represents a group —N—R 3 , R 2 and R 3 can be optionally bound to each other to form, together with the other atoms to which they are bound, a cycle containing from 3 to 6 carbon atoms, saturated, unsaturated, or aromatic, optionally substituted with linear or branched C 1 -C 20 preferably C 1 -C 15 , alkyl groups, said cycle optionally containing heteroatoms such as, for example, oxygen, sulfur, nitrogen, silicon, phosphorous, selenium; —X 1 and X 2 , equal to or different from each other, represent a halogen atom such as, for example, chlorine, bromine, iodine; or they are selected from linear or branched C 1 -C 20 preferably C 1 -C 15 , alkyl groups, —OCOR 4 groups or —OR 4 groups wherein R 4 is selected from linear or branched C 1 -C 20 preferably C 1 -C 15 , alkyl groups.

First claim

The invention claimed is:

1. A process for the preparation of (co)polymers of conjugated dienes which comprises polymerizing at least one conjugated diene in the presence of a catalytic system comprising at least one oxo-nitrogenated complex of cobalt having general formula (I):

wherein:
R 1 and R 2 , independently, represent a hydrogen atom, linear or branched C 1 -C 20 alkyl groups optionally halogenated, cycloalkyl groups optionally substituted, or aryl groups optionally substituted;
Y represents an oxygen atom, or a group —N—R 3 wherein R 3 represents a hydrogen atom, branched C 1 -C 20 alkyl groups optionally halogenated, cycloalkyl groups optionally substituted, or aryl groups optionally substituted;
R 2 and R 3 are optionally bound to each other to form, together with the other atoms to which they are bound, a cycle containing from 3 to 6 carbon atoms, saturated, unsaturated, or aromatic, optionally substituted with linear or branched C 1 -C 20 alkyl groups, said cycle optionally containing heteroatoms;
X 1 and X 2 , independently, represent a halogen atom, or linear or branched C 1 -C 20 alkyl groups, —OCOR 4 groups, or —OR 4 groups wherein R 4 is selected from linear or branched C 1 -C 20 alkyl groups.

2. The process for the preparation of (co)polymers of conjugated dienes according to claim 1 , wherein said catalytic system comprises at least one co-catalyst (b) selected from organic compounds of an element M′ different from carbon, said element M′ being selected from elements belonging to groups 2, 12, 13 or 14, of the Periodic Table of Elements.

3. The process for the preparation of (co)polymers of conjugated dienes according to claim 2 , wherein said co-catalyst (b) is selected from (b 1 ) aluminium alkyls having general formula (II):
Al(X′) n (R 5 ) 3-n   (II)

wherein X′ represents a halogen atom; R 5 is selected from linear or branched C 1 -C 20 alkyl groups, cycloalkyl groups, aryl groups, said groups being optionally substituted with one or more silicon or germanium atoms; and n is an integer ranging from 0 to 2.

4. The process for the preparation of (co)polymers of conjugated dienes according to claim 2 , wherein said co-catalyst (b) is selected from (b 2 ) organo-oxygenated compounds of an element M′ different from carbon belonging to groups 13 or 14 of the Periodic Table of Elements.

5. The process for the preparation of (co)polymers of conjugated dienes according to claim 2 , wherein said co-catalyst (b) is selected from (b 3 ) organometallic compounds or mixtures of organometallic compounds of an element M′ different from carbon capable of reacting with the oxo-nitrogenated complex of cobalt having general formula (I), further comprising extracting X 1 or X 2 of the oxo-nitrogenated complex σ-bound to form at least one neutral compound and an ionic compound, the ionic compound including a cation containing the metal (Co) coordinated by a ligand and a non-coordinating organic anion containing the metal M′, wherein the negative charge is delocalized on a multicentric structure.

6. A process for the preparation of (co)polymers of conjugated dienes according to claim 1 , wherein said conjugated dienes are selected from: 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, cyclo-1,3-hexadiene, or mixtures thereof.

7. The process for the preparation of (co)polymers of conjugated dienes according to claim 1 , wherein in said oxo-nitrogenated complex of cobalt having general formula (I):
R 1 and R 2 , independently, represent a hydrogen atom; or linear or branched C 1 -C 20 alkyl groups;
Y is an oxygen atom or a group —N—R 3 wherein R 3 is selected from phenyl groups substituted with linear or branched C 1 -C 20 alkyl groups;
X 1 and X 2 , the same as each other, are a halogen atom.

8. The process for the preparation of (co)polymers of conjugated dienes according to claim 3 , wherein said aluminium alkyls (b 1 ) having general formula (II) are di-ethyl-aluminium chloride (DEAC), mono-ethyl-aluminium dichloride (EADC), or ethylaluminiumsesquichloride (EASC).

9. The process for the preparation of (co)polymers of conjugated dienes according to claim 4 , wherein said organo-oxygenated compounds (b 2 ) are selected from aluminoxanes having general formula (III):
(R 6 ) 2 —Al—O—[—Al(R 7 )—O—] p —Al—(R 8 ) 2   (III)

wherein R 6 , R 7 and R 8 , independently, represent a hydrogen atom, a halogen atom, or linear or branched C 1 -C 20 alkyl groups, cycloalkyl groups, aryl groups, said groups being optionally substituted with one or more silicon or germanium atoms; and p is an integer ranging from 0 to 1,000.

10. The process for the preparation of (co)polymers of conjugated dienes according to claim 9 , wherein said organo-oxygenated compound (b 2 ) is methylaluminoxane (MAO).

11. The process for the preparation of (co)polymers of conjugated dienes according to claim 5 , wherein said organometallic compounds or organometallic mixtures of compounds (b 3 ) are selected from organic compounds of aluminium and boron represented by the following general formulae:
[(R C ) W H 4-W ].[B(R D ) 4 ] − ;B(R D ) 3 ;Al(R D ) 3 ;B(R D ) 3 P;[Ph 3 C] + .[B(R D ) 4 ] − ;[(R C ) 3 PH] + .[B(R D ) 4 ] − ;[Li] + .[B(R D ) 4 ] − ;[Li] + .[Al(R D ) 4 ] −
wherein w is an integer ranging from 0 to 3, each group R C independently represents an alkyl group or an aryl group having from 1 to 10 carbon atoms and each group R D independently represents an aryl group partially or totally fluorinated, having from 6 to 20 carbon atoms, P represents a pyrrole radical optionally substituted.

12. The process for the preparation of (co)polymers of conjugated dienes according to claim 1 , wherein said process is carried out in the presence of an inert organic solvent selected from: butane, pentane, hexane, heptane, or mixtures thereof; cyclopentane, cyclohexane, or mixtures thereof; 1-butene, 2-butene, or mixtures thereof; benzene, toluene, xylene, or mixtures thereof; methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, 1,2-dichloroethane, chlorobenzene, bromobenzene, chlorotoluene, or mixtures thereof.

13. The process for the preparation of (co)polymers of conjugated dienes according to claim 12 , wherein the concentration of the conjugated diene to be (co)polymerized in said inert organic solvent ranges from 5% by weight to 50% by weight with respect to the total weight of the mixture of conjugated diene and inert organic solvent.

14. The process for the preparation of (co)polymers of conjugated dienes according to claim 1 , wherein said process is carried out at a temperature ranging from −70° C. to +100° C.

Assignees

• Versalis Spa
• Versalis Spa

Inventors

• Ricci Giovanni
• Leone Giuseppe
• Sommazzi Anna
• Masi Francesco

Classifications

• C08F4/704

  Neutral ligand · CPC title

• C08F36/04

  conjugated · CPC title

• C08F36/06

  Butadiene · CPC title

• C08F4/7044

  NNO · CPC title

• C08F136/06 Primary

  Butadiene · CPC title